Chrcooh chrcooh



I Jnited States Patent SUBSTITUTED ALKYLENE DI-AMINO DI-ACETIC ACIDS ANDSALTS Frederick C. Bersworth, Verona, N. I.

No Drawing. Original No. 2,624,757, dated January 6,

1953, Serial No. 193,543, November 1, 1950'. Application for reimueAugust17, 1953, Serial No. 374,838

6 Claims. (Cl. 260-518) Matter enclosed in heavy brackets appears in theoriginal patent but forms no part of this reissue specification; matterprinted in italics indicates the additions made by reissue.

heavy metal In accordance with these objects I have discovered thatalkylene polyamino acids conforming to the general structural formula-CHrC 0 on ous-coon N-alkylena-N CHe-COOH OKs-COOK X X X X xQn-lt-nknne-N-n-Q where X=hydrogen, alkyl, halogen, hydroxyl or alkoxyl; I

where R represents an alkylene radical or an alkylene radical containingether linkages, the resulting polyamino polycarboxylic [acid acquires]acids acquire solubility in organic solvents as well as bactericidal andfungicidal properties in aqueous solutions and [retains] retain strongchelating properties towards heavy metal ions in aqueous as well as inorganic solvent solutions.

The compounds described are all soluble in water in the form of theiralkali metal, ammonia or amine salts. They are not soluble as the acidsin water media but are soluble in organic solvents. The amine salts arealso highly soluble in organic solvents. The chelates are soluble inorganic solvents being non-ionic.

This solubility may be modified particularly as to water systems bymeans of sulfonation in the aromatic ring and/ or alkyl sulfonation inaccordance with known means to form soap-like products.

There are a large number of compounds conforming to this generalstructure given above and the compounds may include mono or polyhalogenated, alkylated, and hydroxylated phenyl groups without departurefrom the invention. As specific examples of the compounds within thescope of the invention the following are given by way of illustrationand not by way of limitation.

Re. 23,904 Reisaued Dec. 14,1954

tion N,N'(2,6 dichloro-4-nitro-] the precipitation of N,N'-

(2,6-dichloro-4-nitro-benzyl) ethylene diamine diacetic acid as thesolid monohydrate. The product is believed to have the formula:

GHs-C 0 OH CHz-COOH 01 I o1 CINQCHrNCHI-CHI-NGHQNOI 1 1 011.0001;cmcoorr at l l at For example, the N02 group in the aromatic nucleus maybe reduced to an amino group, which may then be diazotized and convertedto a halogen by means of the Sandmeyer reaction. Also, the diazoniumsalt may hydrolyzed to a phenolic group by well-known methods.

The amino hydrogens of the phenyl amino group may be substituted byvarious functional groups, such as acetic acid groups to further modifythe properties of the compoun The aromatic [group] groups may also befurther modified by substitution on the aromatic [ring] rings by knownreactions to give derivatives thereof which are valuable chelatingagents.

EXAMPLE II The diazonium salt of Example I is treated with cuprouschloride and excess alkali chloride (Sandmeyer reaction), in the usualmanner, except that a molar amount of cupric ion is used to take care ofthe tendency of the amino acid to combine with copper. The resultingcompound is a chelate of copper, which may be separated from the metalin ethanol solution by treatment with excess HaS. The resulting acid maybe crystallized on evaporation of the solvent, and is believed to havethe formula:

EXAMPLE III The product of Example II may also be obtained [bycondensing 2,4,6 trichlorobenzyl chloride with ethylene diamine, N,N'diacetic acid disodium salt as described in the first step of example]by condensing 2,4,6-trichlorobenzyl chloride with ethylenediamine-N,N'-diacetic acid disodium salt as described in the first stepof Example I. Acidification of the reaction mixture yields the desiredproduct as a crystalline substance.

EXAMPLE IV Two moles of p-chlorophenylethyl chloride,

ClCsHsCHzCHzCl is treated with an aqueous solution of one mole ofdiscdium ethylene diamine diacetate as described in Example I. Onacidification of the reaction mixture the follow ng substance isobtained in crystallizable form:

CHz-OOOH CHs-COOH l (no-curcnrit-onrcnr-N-onronrQOi 7 EXAMPLE V Twomoles of 2-hydroxy-3,6-dichlorobenzyl chloride dissolved in ethanol aregradually added to a gently re- Gem-linemen? C'Hr precipitates from theaqueous solution as the monohydrate (when considerable alcohol ispresent precipitation may be incomplete. Under such conditions it isadvisable to distil off the alcohol solvent).

The precipitated monohydratc product need not be purified for furthersynthesis. However, if desired the hydrate may be recrystallized fromaqueous ethanol. The crude reaction product is then carboxymethylatedaccording to the process of my prior Patents Nos. 2,387,735 and2,407,645 with NaCN and CHzO using about 80% tertiary butyl alcohol asthe solvent and keeping the temperature just below the boiling point ofthe mixture. The product, which is primarily the di-substituted ethylenediamine diacctie acid may be obtained by crystallization from diluteaqueous HCl solution after removal of the tertiary butyl alcohol bydistillation. It has the following structure:

01 on no or [@CHz-N-CEz-CflrN-CIb-O 1 (Lin-coon rLnreoon at on H or Iprefer to use it, however, in the form of its alkali metal salt(somewhat water soluble) directly as obtained from the reaction mixture.It is a strong chelating agent for heavy metal ions.

These compounds are particularly useful, as germicides,

fungicides and/or sterilizing and stabilizing agents (antioxidants) inoily and hydrocarbon systems and emulsions or where it is desired tointroduce the water soluble salt but precipitate the complex fromaqueous solution. The aromatic group also may act as plasticizer inrubber, synthetic rubber. Then the entire molecule follows a stabilizerand plasticizer.

EXAMPLE VI This material may be converted to the desired chelating agentby substitution of two acetic acid (or salt) groups on the aminohydrogens. This may be done by a number of methods; carboxymethylationusing [NaCHz] NaCN and CHzO, treatment with sodium chloroacetate, or[use] by the familiar nitrile method (Strecker synthesis usingformaldehydeyfllfhe carboxymethylation reaction seems to give bestresultsfburrequires a mixed organic aqueous solvent as in Example V. Theresulting disubstituted [ethylene] trimethylene diamine diacetic acid isinsoluble in water and may be obtained by acidification of an aqueoussolution of its salts. It has the formula:

(|J'HrCOOH cnrcoon 01G exams-onion.-crn-u-rennroei In addition to havingstrong chelating properties, it is surface active (as its salts) inaqueous solutions, is a germicide, and the acid and its metal chelatesare soluble in polar and non-polar organic solvents.

It is believed apparent from the above disclosure of genus and speciescompounds falling within the scope of the invention that thedi-(substituted phenyl)-di-alkylene substituted alkylenediam'inediacetic acid compounds of the present invention form a definitegroup of compounds whose chemical properties are closely similar andanalogous though varying somewhat in degree. An analogous series ofcompounds are obtained [where] when the acetic acid groups are replacedby an acetic acid analogue but the chelate-forming properties of thecompounds decrease as the carboxylic groups is moved further away fromthe amino nitrogen by intervening groups. Therefore, I

. prefer to employ theacetic acid group compounds for the chelatingagents of the present invention.

The bactericidal and germicidal properties of these compounds are due tothe halogenated phenyl groups which are substituted in the alkylenegroups displacing the amino hydrogens of the base alkylene polyaminediacetic acid,-

the intervening alkylene group spacing the halogenated phenyl groupsremote from the amino nitrogen sufiiciently to permit same to functionas solubilizing groups in aqueous and organic solvent solutions. Inthese phenyl groups at least one of the hydrogens in the aromaticnucleus must be displaced by a halogen, preferably chlorine, forbactericidal action.

Having hereinabove described the invention generically and specificallyand given several specific examples of the same to illustrate thegeneric scope thereof it is believed apparent that the compounds may bewidely varied structurally without essential departure from theinvention and all such are contemplated as may fall within the scope ofthe following claims.

What is claimed is:

1. A compound conforming to the following formula:

CH|.OO 0H 011213003 X X x X XQR-IL-olkylene-N-RQ wherein R is analkylene group containing from 1 to 5 carbon atoms, alkylene is one ofthe group consisting of three of the X groups being halogen, and thealkali metal, ammonium and amine salts thereof.

6 2. The compound conforming to the structure: 6. The compoundconforming to the structure:

Cl 01 c1 01 I 01 OKs-N-OHrGHn-N-C o1 GHa-N-CHz-CHz-N-CH 5 l l 1 CHrCOOHCHrCOOH- c rCOOH l I References Cited in the file of this patent HYCOOHor the original patent 3. The compound conformmg to the structure: 10UNITED STATES PATENTS am-coon am-coon Number Name -Q- -C 868,294Schmidlin Oct. 15, 1907 4. The compound conforming to the structure: 15

01 0H 0H 01 2,539,212 Strobel et al. Jan. 23, 1951 CHa-N-CHr-ClIz-NFOREIGN PATENTS J Number Country Date 1 HrCOOH moon]! 0! 20 18,095 GreatBritain of 1913 Cl 0H 0H 01 642,244 Germany Mar. 6, 1937 g i, OTHER-REFERENCES Alphen: Chem. Abs., vol. 38, co]. 4943 (1944). C Bischolf etal.: Beilstein (Handbuch, 4m 1. vol. 12,

5. The compound conforming to the following struc HrOOOH HrCOOH HIC 0 OH500 OH

